JPS63223744A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the super contrast photographic characteristics of the titled material by incorporating at least one kind of a specified compd. in a photosensitive silver halide emulsion layer mounted on a supporting body. CONSTITUTION:At least one kind of the compd. shown by formula I is incorporated in the silver halide photographic emulsion layer. The additional amount of the compd. is 2X10<-5>-10X10<-2>mol. per 1mol. of the silver halide. In the formula A1 and A2 are each hydrogen atom, in case that one of said groups is hydrogen atom, another of said groups is sulfinic acid residual group or acyl group, R1 is an aliphatic, aromatic or a heterocyclic group, R2 is hydrogen atom or alkyl, aryl, alkoxy, aryloxy or amino group, G is carbonyl, sulfonyl, sulfoxy, phosphoryl or iminomethylene group, Y is phenylene or naphthylene group, the total of the carbon numbers of R1, R2 and Y groups is >=13. Thus, the negative tone photographic characteristics of the titled material having the prescribed contrast, is obtd. by incorporating a small amount of said compd. in the titled material.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to a silver halide photographic material that provides extremely sharp negative images, highly sensitive negative images, and good halftone image quality, or to direct positive photographic images. The present invention relates to a silver halide photographic material to be formed, and particularly to a photographic material containing a novel compound as a nucleating agent for silver halide.

(Prior Art) Adding a hydrazine compound to a silver halide photographic emulsion or developer is described in US Pat. No. 3,230,727 (Developer with a combination of ascorbic acid and hydrazine). Ko27, J-
No. jZ (using hydrazine as an auxiliary developing agent to obtain a direct positive color image) No. J, j/l, No. 13/ (using β-mono-phenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials) Contains) Same, 4t/Ri, Ri 2! issue, and The Theory of Metographic Process by Mees.
Photography Process), 9th edition (1994J), 2t/page, etc.

Among these, in particular 1 U.S. Pat. Gu/? .

'f7. In No. 11, it is disclosed that a high contrast negative image can be obtained by adding a hydrazine compound.

The patent specification states that a hydrazine compound is added to a silver chlorobromide emulsion. 2. ! It is stated that when developed with a developer having a high pI, extremely high-contrast photographic characteristics with gamma (γ) exceeding /θ can be obtained.
A strong Alzo J IJ developer with a pH close to /3 is easily oxidized in the air and is unstable, and cannot withstand long-term storage or use of 1 liter.

Ultra-high contrast photographic characteristics with gun q exceeding /θ are negative images,
Either way, the positive image is a halftone image (
It is extremely useful for photographic reproduction of continuous w4 images or reproduction of #'i line drawings. ? :,
Conventionally, for the purpose of
Using a silver chlorobromide photographic emulsion having a molecular weight of more than 7J mol, preferably exceeding 7J mol, and developing with an extremely low effective concentration of sulfate ions (usually 0.1 mol, /'l or less) or a hydroquinone developer. The method was commonly used. However, since the sulfite ion concentration in the LLI developer is low in this method, the developer is extremely unstable and cannot withstand storage for more than 14 days.

Furthermore, all of these methods require the use of a silver chlorobromide emulsion with a relatively high silver chloride content, and therefore high sensitivity cannot be obtained. Therefore, there has been a strong demand for using a highly sensitive emulsion and a stable developer to obtain useful power in reproducing halftone images and line drawings and ultra-high contrast photographic characteristics.

The inventors of the present invention have published US Pat.
- No. 79, same evening, 272, No. 79, same evening, 3.2.
? ,t! 1c, such as No. 3, disclosed halogenated @ photographic emulsions that gave extremely high-contrast negative photographic properties using a stable developing solution, but the ace A/hydrazine compounds used in these had some drawbacks. It has been found that there is.

In other words, these conventional hydrazines are known to generate nitrogen gas during the development process, and these gases collect in the film and form bubbles that damage the photographic image. The leakage into the liquid will not adversely affect other photographic materials.

In addition, these conventional hydrazines cause undesirable phenomena such as a marked increase in contrast, simultaneous K, and black spots due to contagious development, which poses a major problem in the photolithography process. For example, a black spot is a black spot that occurs in a place that should be a non-current area between halftone dots, and is caused by the aging percentage of the sensitive material (the aging fatigue of the υ liquid that increases due to storage at high temperatures). etc., due to a decrease in sulfite ions, which are generally used as preservatives, and an increase in pH value, resulting in a significant decrease in commercial value as a photolithographic material.

Therefore, although a great deal of effort has been made to improve these black spots, the improvement of black spots is often limited to sensitivity and gamma (r).
There has been a desire for a silver halide photographic light-sensitive material which has photographic properties that include a decrease in image quality, maintain high contrast sensitivity, and have fewer black spots.

Furthermore, when these conventional hydrazines are required in large amounts for sensitization and high contrast, or when particularly high sensitivity is required in terms of the performance of the photosensitive material, other sensitization techniques (such as chemical sensitization) may be used. U.S. Patent No. 9.2”2.29504 and 4t, 2ri/
When used in combination with a compound that promotes sensitization (such as the addition of a compound that promotes sensitization as described in the Zari issue), sensitization over time and pre-enhancement may generally occur during storage.

Therefore, there has been a desire for a compound that can reduce the generation of bubbles and leakage into the developer, has no problems with stability over time, and can provide extremely high-contrast photographic properties with the addition of a very small amount. .

Also, US Patent No. Q, 3r, t, /θ1, same.

No. 269.922 describes that extremely high contrast negative tone photographic properties can be obtained by using hydrazines having substituents that are easily adsorbed to silver halide grains.
Among these hydrazine compounds having an adsorptive group, those specifically mentioned in the above-mentioned known examples have the problem of causing desensitization over time during storage. Therefore, it was necessary to select a compound that would not cause such problems.

On the other hand, there are various direct positive photography methods, including a method in which silver halide grains that have been fogged in advance are exposed to light in the presence of a desensitizer, and then developed, and a method in which silver halide grains are exposed to light in the presence of a desensitizer and then developed, The most useful method is to develop the silver oxide emulsion in the presence of a nucleating agent after exposure. The present invention relates to the latter.

Silver halide emulsions that mainly have photosensitive nuclei inside silver halide grains and in which latent images are mainly formed inside the grains are called internal latent image type silver halide emulsions. They are distinguished from silver halide grains that form latent images.

A method for directly obtaining a positive image by surface developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent, and a photographic emulsion or light-sensitive material used in such a method are described, for example, in U.S. Pat. No. 1, 4t. tt, ri No. 13, same, 92
No. 7.273, λ, Geta 21?7.6, λ, re
♂? ? No. 2, same! ? 2.2! θ, same, Otsu 77
．． No. 371, 3° Cocoa, No. 111, j, j/
No. 7.7.22, British Patent/, 0//, 01. ．． No. 2,
same/,/! /, Jg3, same/, 2t9.44tO, same, θ//.

39! No., Special Public Show 4t3-Kota, Guθ! No., Mawarita,
! ? , /44 issue, JP-A-Shoj3-/, 4,423, same/3? , No. 733, No. j4t-47.73-, No. j
4t-410, 6λ, J-4t-7da, 136, r4t-74t, 7λ, jj-jλ, Q! !
Same issue! ! It is known as -taO1riaOgo.

In the above-mentioned method for obtaining a direct positive, the nucleating agent may be added to the developer, but it can be added to the photographic emulsion layer or other appropriate layer of the light-sensitive material so that it is adsorbed onto the surface of the silver dihalide grains. When this is done, good inversion characteristics can be obtained.

The nucleating agent used in the above-mentioned method for obtaining a direct positive is disclosed in US Patent No. 2. ! 4! , 7rJ-No., same, t
r/, hydrazines described in No. 922, and U.S. Patent No. 3.1 Core,! ! - hydrazides and hydrazi-based compounds described in US Patent No. 3. Bu/J-, 4
/j issue, 3.7/ri, 41.94 issue, same, ? ,7
3 (<, No. 731, 4t.

No. 094t, 623 and same g, //j, /, 22, British Patent No. 1. Ko/J, rJt issue, Tokukai Sho! Cor 3
Da 2≦ issue and the same! --Heterocyclic 9th class salt compounds described in US Pat. No. 69673, US Pat.

No. 923, Dohiro, θ3/, /Core No., Same, /3ri, 3
/ No. 7, 4t, No. 037, same.

2! Thiourea-bonded acylphenylhydrazine compounds described in Ji, No. 111 and q, λ2, 3dμ, British Patent No. 2,0/X, 41413, etc., and U.S. Patent No. Q, 010.207. Compounds having a heteroterminous thioamide as an adsorption group described in British Patent Nos. λ, θ/
A phenylacylhydrazine compound having a heterocyclic group having a mercapto group as an adsorption type described in US Pat. No. 3.77! , 4t70, a sensitizing dye having a substituent with a nucleating effect in its molecular structure, JP-A-Sho! Tar〇0.230, same! Tar 2/λ, ♂, 2/ issue, same! 9-J/J, No. 129, Re5earchDi
A hydrazine compound described in ``Sclosure'' No. λ3j10 (July 1913) is known.

However, all of these compounds had insufficient activity as nucleating agents, and those with high activity had insufficient preservability, and their activity did not increase after they were added to the emulsion before coating. There were drawbacks such as fluctuations in the film quality and deterioration of film quality when added in even larger amounts.

(Objects of the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining photographic properties of extremely high contrast negative gradation with a gamma exceeding 70 using a stable developer. It is to be.

The first object of the present invention is to provide a negative-working halogenated compound containing acylhydrazines that does not adversely affect photographic performance and can provide the desired photographic properties of extremely high contrast negative gradation with a small amount of addition. An object of the present invention is to provide a silver photographic material.

A third object of the present invention is to provide a direct positive silver halide photographic material containing a highly active nucleating agent.

The object of the present invention is, firstly, to contain hydrazines which are easy to synthesize, have small activity fluctuations during the production of sensitive materials, have excellent storage stability, and do not cause deterioration of film quality when added in large amounts, and are stable over time. It is an object of the present invention to provide a silver halogenide photographic X-sensitive material with good quality.

The first object of the present invention is to provide a silver halogenide photographic light-sensitive material which exhibits ultra-high contrast photographic properties [2] and which has less occurrence of black spots.

(Means for Solving the Problems) An aspect of the present invention is to provide a silver halide photographic light-sensitive material having at least seven silver halide photographic emulsion layers, in which the photographic emulsion layer is represented by the following general formula (I). This was achieved by including at least one species of the compound.

General formula (I) In the formula, A! , A2 essentially represents a hydrogen atom, or one hydrogen atom and the other a sulfinic acid residue or acyl group, and R1
represents an aliphatic group, an aromatic group or a heterocyclic group, and R2
represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an amine group, and these groups may be substituted.

G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an N-substituted or unsubstituted iminomethylene group, and Y represents a phenylene group or a naphthylene group, and these phenylene and naphthylene groups may be substituted or not. good.

The total number of carbon atoms in R1, R2 and Y is 73 or more.

Next, the general formula (1) will be explained in detail.

81% in general formula (1) IC A2 is a hydrogen atom, an alkylsulfonyl group having 2Q or less carbon atoms, and an arylsulfonyl group (preferably a haphenylsulfonyl group or a sum of Hammett's substituent constants of 10, ! or more) (a phenylsulfonyl group substituted so that Straight chain, branched or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbo/amide groups,
Examples include hydroxyl group, carboxy group, and sulfonic acid group. ) A hydrogen atom is most preferable as A1 and A2.

In general formula (1), the aliphatic group represented by R1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R1 is a monocyclic or 2m aryl group, such as a phenyl group or a naphthyl group.

The heterocycle of R1 includes N, 0. or a 3-/θ-membered saturated or unsaturated heterocycle containing at least one S atom, which may be a single ring or may be a fused ring with another aromatic ring or heterocycle. may be formed. Preferably as a heterocycle! Preferably, it is an aromatic heterocyclic group having several members, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an inquinolinyl group, a thiazolyl group, and a benzthiazolyl group. .

R1 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkoxy groups, aryl groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups,
Examples include sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, and carboxyl group.

These groups may be bonded to each other to form a ring, if possible.

Preferred as R1 is an aromatic group, more preferably an aryl group.

Among the groups represented by R2, when G is a carbonyl group, preferable ones include a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group). etc.), aralkyl groups (e.g. 〇-hydroxybenzyl group etc.), aryl groups (e.g. evaphenyl group, 3.j-') chlorophenyl group, 0-methanesulfonamidophenyl group, goomethanesulfonylphenyl group ), hydrogen atoms are preferred in %.

In addition, when G is a sulfonyl group, %R2 is an alkyl group (e.g. methyl group, etc.), an aralkyl group (e.g. 0-hydroxyphenylmethyl group etc.), an aryl group (e.g. phenyl group etc.) or a substituted amino group (e.g. dimethylamino group etc.). etc.) are preferred.

When G is a sulfoxy group, R2 is preferably a cyanobenzyl group or a methylthiobenzyl group, and when G is an N-substituted or unsubstituted iminomethylene group, R2 is preferably a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group. It is the basis.

When G is a phosphoryl group, %R2 is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, with a phenoxy group being particularly preferred.

As the substituent for R2, in addition to the substituents listed for %R1, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a yanitro group, etc. can be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may form a ring connected to each other.

R1 or R2, especially R1, preferably contains a diffusion-resistant group such as a coupler, a so-called ballast group. This ballast group has two or more carbon atoms and is composed of a combination of one or more of an alkyl group, a phenyl group, an ether group, an amide group, a ureido group, a urethane group, a sulfonamide group, a thioether group, and the like.

The total number of carbon atoms of R1%R2 and Y is 73 or more,
Preferably it is 2/ or more.

Here, if the total number of carbon atoms is less than /-, black spots are likely to occur.

As the substituent for Y, the groups listed for %R1 and R2 and their substituents can be applied.

Furthermore, the -SO□NH- group in general formula (I) may be substituted at any of the o, m and p positions with respect to hydrazine, but the p position is more preferable.

G in general formula (1) is most preferably a carbonyl group.

Specific examples of the compound represented by general formula (1) are shown below.

However, the present invention is not limited to the following compounds.

C3H7(n) /q H3 /j 3θ 3koUki3 Next, a typical method for synthesizing the compound of the above general formula (1) will be explained by giving a synthetic example.

Synthesis Example / Synthesis of Compound / Under a nitrogen atmosphere, -1(4t-aminophenyl)-7-formylhydrazine-0tg was dissolved in N,N-dimethylformamide/σm/, and then triethylamine-,/
m was added and -j'CK was cooled. To this, Hiro (, Z,
4t-di-tert-pentylphenoxy)-/-butylsulfonyl chloride! , /g in /θml of acetonitrile was added dropwise. During this time, the liquid temperature was 0°C.
The mixture was cooled and stirred so as not to exceed the temperature. After continued stirring at o'C for 7 hours, the mixture was poured into ice water and extracted with ethyl acetate.

The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the P solution was concentrated. The concentrate was separated and purified by silica gel column chromatography (developing solvent: ethyl acetate/chloroform = 2//(volj
/ vat)) I got what I was looking for.

Yield: 7 g Oil Synthesis Example 2 Synthesis of Compound A: Synthesis of (1), 2-(gu(3-nitrobenzenesulfonamido)phenyl)-/-formylhydrazine Under nitrogen atmosphere, !-(4t-aminophenyl )-/-To 4t and 24g of formylhydrazine, add and dissolve 10ml of N,N-dimethylformamide/acetonitrile♂ and 2?g of triethylamine, and dissolve -j 'CIC1
lllL metanitrobenzenesulfonyl chloride gokoj
g was gradually added. During this time, the mixture was stirred while being cooled so as not to exceed the liquid temperature -z'C.

After further stirring at -r'C or lower for 5 hours, the mixture was brought to room temperature and extracted with ethyl acetate and saturated brine.

The organic layer was separated, concentrated to a volume of 100 ml, and then 3 portions of n-hexane were added. After stirring at room temperature for 30 minutes, the resulting crystals were collected and washed with 00 ml of ethyl acetate.

Yield: 4tOg Melting point/ri/~/ri3'C2-(2)
, 2-[<t-(3-aminebenzenesulfonamido)phenyl]-/-formylhydrazine synthetic iron powder I? Og, ammonium chloride4. rg, Improper Tools 4. ．． jl and water λ and 2j were mixed and heated and stirred on a steam bath. This is the nitro compound tt obtained in K(1)
Og was added (-5/, and refluxed for 1 hour. Then, insoluble matter was filtered, and the liquid was concentrated under reduced pressure, and water was added. The crystals formed were collected and poured with Impropatool/l. Wash it again.

Yield J3J'g Melting point/! ! ~/! IoC Co(3)
Synthesis of 2-Cter(3-phenoxyamidobenzenesulfonamido)fer;]-/-formylhydrazine Under a nitrogen atmosphere, the amino compound obtained in (2) 4t! After dissolving θg with N,N-dimethylacetamide J, J”13,
After cooling to below -t'C and adding 7.2 Cml of pyridine, 30 g of phenyl chloroformate was added dropwise. During this time, the mixture was stirred while being cooled so that the liquid temperature did not exceed -t'C.

After further stirring for 7 hours at a temperature below t'C, the reaction solution was added dropwise to a saturated saline solution (stirred for 7.30 minutes). The resulting crystals were collected and then washed with water.

Yield d//g Melting point/9! ~/97°C, 2-(4)
Synthesis of compound 2y Under nitrogen atmosphere, 3-(,z,4t-di~tert
-Hentylphenoxy)-/-fropylamine 3.2g
and imidazole/Δ'g in 30ml of acetonitrile,! It was heated to θ0C. The urethane compound obtained in (3) J, Oml c7) N, N -
Drop a solution dissolved in dimedelyl heptamide, and
The mixture was heated and stirred at C for 1 hour. After cooling to io Oc (-, θ, j mol/l of hydrochloric acid/l and ethyl acetate/l
injected into the mixture. The organic layer was separated and concentrated, and diluted with a mixed solvent of ethyl acetate and n-hexane (vol/vol).
= , 2 / , t).

Yield J3. tg Melting point //J' ~ /2/ 0C (softening) Synthesis example 3 Synthesis of compound / under nitrogen atmosphere, Co(couaminophenyl) -/-''r
Cetylhydrazine λ,! g was dissolved in N,N-dimethylformamide/θml 1-1, then triethylamine 2°/ml was added, and the mixture was cooled to -J-'C. This is icg-
c, 4t-tert-inchylphenoxy)-/
A solution of -butylsulfonyl chloride f, J'g dissolved in /θml of acetonitrile was added dropwise. During this time, the mixture was cooled and stirred so that the liquid temperature did not exceed 0°C. After stirring continuously at θ0C for 7 hours, the mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the r solution was concentrated. @ Separate the fine particles by silica gel column chromatography ff1ll (
Developing solvent: ethyl acetate/ionform = 2//
(vol/vol)) to obtain the desired product.

Yield 3. ．． 2g oil synthesis inversion Synthesis of compound xg Under a nitrogen atmosphere, 70.6g of co(3-aminophenyl)-/-formylhydrazine was dissolved in 30mal of N,N-dimethylformamide, and then triethylamine! ,
and cooled to -z'C. Goo to this (
,2, p-G tert-inchylphenoxy)-/
A solution of 3 g of -butylsulfonyl chloride// dissolved in 20 ml of acetonitrile was added dropwise. During this time, the mixture was cooled and stirred so that the liquid temperature did not exceed θ0C. After stirring continuously at θ0C for 7 hours, the mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the r solution was concentrated.

The concentrate was separated and purified by silica gel column chromatography (developing solvent: ethyl acetate/chloropol, b, =,
2/y (vol/vol))t, the target product was obtained.

Yield/2, cog Solidified product synthesis example! Synthesis of compound t-(1)/-(2-chloro-ternitrophenyl)hydrazine Hydrazine hydrate at room temperature under nitrogen atmosphere! Dissolve 9 ml in 77 totrile 7/2 ml 1-1 then /, 2-
Dichloroogu nitrobenzenta.

A solution of 3 g dissolved in acetonitrile 7/ml was added dropwise. After completion of the dropwise addition, the reaction mixture was heated under reflux for a period of time to concentrate the reaction solution. water! Add θOml, collect the resulting crystals, add acetonitrile and θθml, and collect.

After heating under reflux for a minute, the mixture was cooled on ice to room temperature, and the crystals were collected.

Yield core g j -(2) Synthesis of two(,2-chloro-goonitrophenyl)-/-formylhydrazine Under nitrogen atmosphere, hydrazine compound 27 obtained in (1)
Dissolve g in acetonitrile/6θm, then formic acid/
4tmJl was added dropwise. After heating under reflux for one hour, the mixture was cooled on ice, and the resulting crystals were collected and washed with acetonitrile.

Yield -20,,1g j-(3),2-(guamino-two-chlorphenyl)
-/- Synthesis of formylhydrazine Nitro compound obtained in (2) under nitrogen atmosphere.

! g1 iron powder (7g% ammonium chloride - 2g1 inproper tool 4tooml and water λθml mixed,
The mixture was stirred at reflux for 2 hours on a steam bath. Then, the insoluble matter is heated to r
After filtration, the P solution was concentrated under reduced pressure to about 100 ml, and then cooled on ice. The resulting crystals were collected and diluted with isoprono-hair alcohol.
oml and washed.

Yield//, Og j-(4) Synthesis of compound 5-(4t-aminochloruphenyl)-/-formylhydrazi/r, trg under nitrogen atmosphere, N,N-
Dissolved in 30ml of dimethylformamide, then added 3.03g of triethylamine, -! Cooled to 0C. A solution of 9-(co, 4t-tart-pentylphenoxy)-/-butylsulfonyl chloride//, /g dissolved in /θml of acetonitrile was added dropwise to this.

During this time, the mixture was cooled and stirred so that the liquid temperature did not exceed 0°C. After stirring for 7 hours at θ0C, the mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the r solution was concentrated. The concentrate was separated and purified by silica gel column chromatography (developing solvent: ethyl acetate/chloroform =//co(v
o//vol)) L, the target product was obtained.

Yield, og Melting point/J-7-719oC Synthesis Example d
Compound! Synthesis of j-(1) 2-chloro-i-diethylsulfamoyl-! -Synthesis of Nitrobenzene Cochrolu! - After dissolving 6 g of nitrophenylsulfonyl chloride in acetone, -1o0
3.03 g of triethylamine and diethylamine, 2. ．． A solution of 2 g dissolved in 20 ml of acetonitrile was added dropwise. During this time, the mixture was cooled and stirred so that the liquid temperature did not exceed 0°C. The temperature was gradually raised to room temperature, and the mixture was poured into pHH2C diluted hydrochloric acid water. Collect the formed crystals and wash with water.9.

Yield 7. /g, 4-(2) /-(-2-diethylsulfamoylda-ditrophenyl)hydrazine Synthesis (1) The chloride obtained in Oml of methanol was dissolved in 0 ml of methanol, heated to reflux, and hydrazine- 3 ml of hydrate 6°
A solution of gm/gm in ethanol was added dropwise. After further refluxing for 9 hours, the reaction solution was concentrated to obtain the desired product.

Yield 7. /g Otsu-(3) Synthesis of 2-(cordiethylsulfamoyl-Hiro-nitrophenyl)-/-formylhydrazine The hydrazine compound obtained in (2) under a nitrogen atmosphere! g
was dissolved in 2 ml of acetonitrile, then 2 ml of formic acid.
1 liter was added dropwise. After heating under reflux for 1 hour, it was concentrated under reduced pressure.
100 ml of water was added and stirred at room temperature for 7 hours. The resulting crystals were collected and re-solidified with ethanol.

Synthesis of θg j -(4), 2-(4t-amino-1-diethylsulfamoylphenyl)-/-formylhydrazine Under a nitrogen atmosphere, 70 g of the nitro compound obtained in (3) was added to 210 ml of ethanol and water. A solution of 7 g of hydrosulfide J dissolved in water/-θm/ was added dropwise thereto. After stirring at room temperature for 30 minutes, further stirring at 60°C/! Stir for a minute. After removing insoluble matter by filtration, the r solution was concentrated under reduced pressure, 100 ml of water was added, and the resulting crystals were collected and reconsolidated with ethanol.

Yield 3.7g 6-(5) compound! Under a nitrogen atmosphere, 7.7 g of the amine compound obtained in (4) was dissolved in 77 ml of acetonitrile, and the mixture was heated to reflux.
/-butylsulfonyl chloride, /g. A solution dissolved in 1 ml of acetonitrile was added dropwise. After further heating under reflux for 7 hours, the mixture was poured into 20θmlj of water (7 hours).

The supernatant was removed, and n-hexane was added to solidify, and the n-hexane in the supernatant was further removed and washed with ether to obtain the desired product.

Yield/, 4tg Melting point/49-/7/'C In order to incorporate the compound of the present invention into the silver halide emulsion layer, after dissolving the compound of the present invention in water or a water-miscible organic solvent, ( If necessary, alkali hydroxide or tertiary amine may be added to form a salt (may be dissolved in 17), and added to a silver halide emulsion (at this time, if necessary, acid or alkali may be added to adjust the pH). Even if you adjust it (↓).

The compounds of the present invention may be used alone or in combination of two or more. The amount of the compound of the present invention added is #)/x/θ-5~/X/θ-2 mol per mol of silver halide, preferably 70-5 mol~/X10-2 mol. An appropriate value can be selected depending on the properties of the silver halide emulsion to be combined.

The compound represented by formula (i) of the present invention can form a high-contrast negative image when used in combination with a negative emulsion. On the other hand, it can also be used in combination with an internal latent image type silver halide emulsion. The compound represented by the general formula (1) of the present invention is preferably used in combination with a negative emulsion to form a high-contrast negative image.

When the silver halide is used to form a negative image with high film resistance, it is preferable that the average grain size of the silver halide used be fine (for example, 0.7μ or less), especially θ,! It is preferably less than μ. There is basically no limit to the particle size distribution, but
Monodispersity is preferred. Monodisperse here means at least that amount in terms of weight or number of particles! This means that a group of particles is composed of a group of particles whose size is within 0% of the average particle size.

Silver halogenide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or may have irregular crystal structures such as spherical and plate shapes.
It may have crystals such as gular or a composite of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Formed separately. Two or more silver halide emulsions may be mixed and used.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

Particularly suitable silver halide for use in the present invention is prepared in the presence of Q-8 to 10-5 moles of iridium salt or complex salt thereof per 7 moles of silver, and the silver iodide content on the grain surface is The silver iodide content is larger than the grain average silver iodide content. When an emulsion containing such silver iodide is used, photographic characteristics with higher sensitivity and higher gamma can be obtained.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. A specific example is US Patent No. 2. <t4tr
, otsu θ, British patent no./! , θ≦/, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

In the above case, it is desirable to add the above-mentioned iridium salt before the completion of physical ripening of the silver halide emulsion, particularly during grain formation.

The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (III), potassium hexachloroiridate (IV), ammonium hexachloroiridate (It), etc. There is.

In the present invention, the silver halide emulsion layer is
/the law of nature? It is preferable to include two types of monodispersed emulsions with different average particle sizes as disclosed in Japanese Patent Application Sho≦0-2320♂B from the viewpoint of increasing the maximum density (Dmax).
The small-sized monodisperse particles are preferably chemically sensitized, and the most preferred method of chemical sensitization is sulfur sensitization. The dog size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Generally, large-sized monodisperse particles are not subjected to chemical sensitization because they tend to generate black spots, but when chemical sensitization is carried out, it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur. Here, "shallow application" means chemical sensitization for small particles by shortening the chemical sensitization time, lowering the temperature, and reducing the amount of chemical sensitizer added. . There is no particular limit to the sensitivity difference between a large-sized monodispersed emulsion and a small-sized monodispersed emulsion, but ΔlogE is 0. / to /, 0, more preferably 0.2 to 0.7°, and the higher the dog size monodispersed emulsion, the better.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative and adding sulfite ions to 0. /! It is obtained when processing with a developer having a pH of 10.z to 72.3 and containing mol/1 or more.

The average grain size of the small monodisperse grains is 90% or less, preferably 10% or less, of the average grain size of the large monodisperse silver halide grains.

The average grain size of the silver halide emulsion grains is preferably from 0.0 μm to 0.0 μm, preferably from 0°7 μm to 0.7 μm. j
It is preferable that the average particle size of dog-sized and small-sized monodisperse particles is included in this range.

In the present invention, when one or more emulsions of different sizes are used, the amount of coated silver of the small-sized monodisperse emulsion is preferably 4 tO to σwt, more preferably! θ~rowt.

In the present invention, monodispersed emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into separate layers.

When they are introduced into separate layers, it is preferable to place the large emulsion in the upper layer and the small emulsion in the lower layer.

The total coating silver amount is preferably /g/m2 to /g/m2.

The photosensitive material used in the present invention includes Japanese Patent Application Publication No. Sho! j-jλ03-0 No. 4t! page~! The sensitizing dyes described on page 3 (for example, cyanine dyes, merocyanine dyes, etc.) can be added.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
74 volumes/7
4413 (Published February 2017), page 23, Section 5, ■.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing capri or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines: mercaptotriazines; thioke compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly couhydroxysubstituted (/, , v, 3a, 7
) tetrazaindenes), pentaazaindenes, etc.;
A number of compounds known as anti-caprylic agents or stabilizers (1) can be added, such as benzene thiosulfonic acid, benzene, sulfinic acid, benzene sulfonic acid amide, etc. Therefore, it is preferable to use (7) benzotriazoles (e.g., j-methyl-bencitriazole) and nitroindazoles (e.g., nitroindazole). good.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the other hydrophilic colloid layer of the photographic emulsion. For example, chromium salts, aldehydes (formaldehyde, geltaraldehyde), N-methylol compounds (dimethylol urea, etc.), activated vinyl compounds (/,
J', J--) lyacryloyl-hexahydro-5-
) riazine, /, 3-vinylsulfonylruco--prohanol f! nido), active halogenated compounds (s, g-cyclo-6-hydroxy-8-triazine)
, mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

The surfactant preferably used in the present invention has a molecular weight of 30 as described in Japanese Patent Publication No. 3/997.2.
0 or more polyalkylene oxides. When used as an antistatic agent, 1c is a fluorine-containing surfactant (for details, refer to U.S. Pat. Particularly preferred is the ``dajj'ri''.

The photographic material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion 1 and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate +-, alkoxy acrylic (meth)acrylate, glycidyl (
Polymers containing meth)acrylate alone or in combination, or combinations thereof with acrylic acid, methacrylic acid, and the like as monomer components can be used.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Examples of compounds having acid groups include polymers or copolymers having repeating units of organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acid monomers such as acrylic acid, maleic acid, and phthalic acid. Regarding these compounds, please apply for a special application for 6/7? No., the same θ−
6/173, same θ-/Otsu No. 3734, and same Otsu 0-
/ri64! The description in the specification of No. J' can be used as a reference. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and as a high molecular compound, acid monomers such as acrylic acid and crosslinkable monomers having two or more unsaturated groups such as divinylbenzene are particularly preferred. A water-dispersible latex of a copolymer consisting of -mer.

In order to obtain ultra-high contrast and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or a pH/ ,?
It is not necessary to use a highly alkaline developer close to that of 100%, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.7 mole/1 or more of sulfite ion as a preservative, and has a pH of
/ 6i, r-/, 2, j, special 1c p H
A sufficiently high-contrast negative image can be obtained by using a developer having a ratio of //, θ to /ko, 0.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, as it is easy to obtain good halftone dot quality. Combinations of pyrazolidones or dihydroxybenzenes and p-amine phenols may also be used.

The developing agent is usually 0.0 tmol/l to 0.0 tmol/l. Preferably, it is used in an amount of ♂mol/l. In addition, when using a combination with dihydroxybenzenes /-phenyl-3-bira/IJtons or p-amine-phenols, the former is 0.0 t mol/l-0゜j mol/It, and the latter is 0.0 t mol/l-0゜j mol/It. .01
Preferably, it is used in an amount of mol/l or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is 0.4 t mol/j1 or more, especially 0.4 t mol/j1 or more. jmorph 11
The above is preferable.

The developing solution of the present invention contains JP-A Shojj-J as a silver stain preventive agent.
(The compounds described in Japanese Patent Application No. 7,3417 can be used.
The compounds described in No. 74tj can be used.

In addition, as a pH buffering agent for developing solutions, JP-A-40-9
3.4 Compounds described in tj No. 3 or patent application Shoj/-,
The compounds described in 2/, 7θ♂ can be used.

The compound represented by the general formula (1) can be used in combination with a negative emulsion in a high-contrast photosensitive material as described above, and can also be combined with an internal latent image type silver halide emulsion. state

The content of the compound represented by the general formula (1) in the emulsion layer is such as to give a sufficient maximum density (for example, silver concentration /, 0 or more) when the internal latent image type emulsion is developed with a surface developer. Preferably in quantity.

In practice, the appropriate content can vary over a wide range as it depends on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but 1 mole of silver is about O1θθjmg!
A range of θomg is useful in practice, preferably from about O0θ/mg to about 100 mg per mole of silver. Regarding the definition of internal latent image disc and silver halogenide emulsion, see JP-A-Shoj/-/
7θ733 Publication No. 1θ page upper column and British Patent No. 1, or
It is described in Publication No. 9°017, page 1/0 to page 0.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. Sensitizing dyes include cyanine dye, merocyanine dye, complex cyanine dye, and complex merocyanine color L holopolar.
Cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. These sensitizing dyes include, for example, JP-A Shoj Day 4.
to, tJe issue, same! Tata ao, t3 issue and the same Tata J
This includes the cyanine dyes and merocyanine dyes described in No. 73.

The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, it can be developed with a developer containing a color image-forming coupler.

Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are given in Research Disclosure (RD)/74 G3 (/7/year/-month) ■-D and Nf/7 (/74). (July 1979).

Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler.

In the present invention, it is preferable to use divalent yellow couplers, and representative examples thereof include yellow couplers that eliminate oxygen atoms or yellow couplers that eliminate nitrogen atoms. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! The -pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamine group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.

Nimura amount! - As the leaving group of the pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. preferable. Also European Patent No. 7
3. It has a pallast group as described in No. lrj! - Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, US Patent No. ?
, 77? , 15', preferably pyrazolo (:z, /-e)[:/,,2. Q
]) Liazoles, Research Disclosure λ4
Virazolotetrazoles and Research Disclosure J4tλ3 described in tcoλQ (/ji?y April 2013)
Examples include pyrazolopyrazoles described in 0 (/te/4 is year g month). The imidazo(/, 2-b'l pyrazoles described in European Patent No. 1/9,7417 are preferred from the viewpoint of low yellow side absorption of the coloring dye and light fastness. ?Pyrazolo [/.

z-b](/, z, 4t:I) lyazole is particularly preferred.Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, as disclosed in US Pat. No. 2, 4t7Q.

293, preferably the naphthol couplers described in U.S. Pat. No. 9.0521.272, 9°/4t4.
Issue 39A, same issue, here! Typical examples include two-equivalent 7-toll couplers of the oxygen atom elimination type described in Kota No. 33, Kota Otsu, and No. 0θ. Also, specific examples of phenolic couplers are U.S. Patent Nos. 2 and 34?
, No. 922, No. 2.707.171, No. 2.77
2,76.2, same No. 2. r93', No./26, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3.7? A phenolic cyan coupler having an alkyl group equal to or higher than an ethyl group at the meta position of the phenol nucleus described in Ko, No. 002, a co, j-diacyl amino substituted phenol coupler, and a phenylureido group at the 2-position and! These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in US Pat. No. a, ztt.

No. 237 and British Patent No. ko, /ko! ,! Specific examples of magenta couplers are given in European Patent No. 70 and European Patent No. Zorro, 670.
No. and West German application publication cylinder 3,234 tons.

! No. 33 describes specific examples of yellow, magenta or cyan couplers.

Dye-forming couplers and the special couplers mentioned above may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in US Pat. No. 3,4t! /, 1
No. 20 and No. 9. θro.

It is described in No. 277. Specific examples of polymerized magenta couplers are described in British Patent No. 102,773 and US Pat. No. 4,347.272.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in two different layers. It is also possible to introduce more than one.

The standard usage amount of the color coupler is in the range of υQ, θθ/ to 1 mole per mole of photosensitive silver halide, preferably 0.0/ to 0.0% for the yellow coupler.
j mole, 0 for magenta coupler, OC# to 0.
3 moles, and for cyan couplers θ, Q02 to 0.
It is 3 moles.

In the present invention, developing agents such as hydroxybenzenes (eg, hydroquinones), aminophenols, 3-pyrazolidones, etc. may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention is subjected to appropriate development processing in combination with a dye image-providing compound (c coloring material) for color diffusion transfer that releases a diffusible dye in response to development of silver halide. It can also be used later to obtain a desired transferred image on the damaged layer. Many coloring materials are known for use in color diffusion transfer methods. It is preferable to use a type of colorant that is cleaved to release a diffusible dye (hereinafter abbreviated as DRR compound). Among them, DR having an N-substituted sulfamoyl group
R compounds are preferred. 4IIC.

Preferred for use in combination with the nucleating agent of the present invention are U.S. Pat. O- as described in No. J-- etc.
DRR compounds having hydroxyarylsulfamoyl groups and JP-A-Sho! J-74t.

It is a DRR compound having a redox core as described in No. 32/. When used in combination with such an RR compound, the temperature dependence particularly during treatment is significantly small.

Specific examples of the DRR compound include those described in the above patent specification, magenta dye, and image-forming substances such as /-hydroxy-cochtramethylenesul7amoyru-a-(J'-methyl-q'-( Co “- Hydroxida”
-Methyl-! "-hexadecyloxyphenylsulfamoyl)-phenylazo]-7talene, as a yellow dye image-forming substance /-phenyl-3-cyano-4t+
λ″′, ri″′-tert--<methylphenoxyacetamino)-phenylsulfamoyl]phenylazo)-! Examples include pyrazolone.

A light-sensitive material using the internal latent image type emulsion of the present invention can directly obtain a positive image when developed using a surface developer. The development process with the surface developer is substantially k.
, which is induced by latent images or capri nuclei on the surface of silver halide grains. Although it is preferable that the developer does not contain a silver halide solubilizer, as long as the internal latent image does not substantially contribute to the completion of development by the surface development center of the silver halide grains, (for example, sulfites) may be included to some extent.

In order to develop the light-sensitive material using the internal latent image type emulsion of the present invention, various known developing agents can be used.

Examples of the present invention are shown below, but the present invention is not limited thereto.

(Example) The present invention will be explained in detail by way of examples below.

Example/ Emulsions (A) and CB) were prepared as shown below.

[Emulsion A]

1 mole of silver in gelatin aqueous solution kept in zooc? )4t
x In the presence of 10-7 mol of iridium hexachloride and ammonia, silver nitrate aqueous solution, potassium iodide, and potassium bromide aqueous solution were simultaneously added at 11C for 60 minutes, and the pAg during that time was reduced to 2.
．． A cubic monodisperse emulsion having an average grain size of 0.3 .mu.m and an average silver iodide content of 1 mol was prepared by maintaining the average grain size at .

[Emulsion B]

The amounts of potassium iodide and ammonia were adjusted in the same manner as in Emulsion A to obtain an average grain size of O, λμ, and average silver iodide content of 0.
．． A 1 mol-㎜ cubic monodisperse emulsion was prepared. Emulsion A, B
In both cases, desalination was performed using the flocculation method.

Emulsion B was then subjected to sulfur sensitization using hypo to prepare a sulfur sensitized emulsion having an average grain size of 0.2 λμ and an average silver iodide content of 0.7 molar cubic monodisperse.

j as a sensitizing dye in these silver iodobromide emulsions.

Sodium salt of j'-cycloterethyl-3,37-bis(3-sul7oprovil)oxacarbocyanine, terhydroxy-4-methyl-/, as a stabilizer! ,
3a, cootetrazaindene, aqueous latex (a) represented by the following structural formula, aqueous latex (a) CI (3 dispersion of polyethyl acrylate, /, 3-divinylsulfonyl-coprobanol t-added* After, emulsion A,
B was mixed in a ratio of silver halide weight ratio/; q, and the compound of the general formula (1) of the present invention was added as shown in Table 1, and then polyethylene terephthalate was added. Coating was carried out on the film so that the amount of silver was 3.4 tg/m2. Each sample was exposed and developed, and photographic properties were measured.

The results are shown in Table 1.

Note that a developer having the following formulation was used.

Developer formulation Hydroquinone 4t, t, ogN
-Methyl-p-7 minophenol//Cosulfate θ,/g Sodium hydroxide 72.0g Potassium hydroxide
3.9.0g monosulfosalicylic acid
4t! , 0g boric acid
21.0g potassium sulfite /10
．． , θg ethylenediaminetetraacetic acid disodium salt /, 0g potassium bromide, θg! -Methylbenzotriazole 0.4
gn-butyljetanolamine
is, add 0g water //, adjust to pH=//, 1θ.

The unit of the ax addition amount is 1 mol Ag.

-x-+ γ is (3, o-0, 3)/(log(+!
Once! , 0) - 1og (exposure amount that gives a density of 0.3)).

←Major Halftone dot quality is visually evaluated at J level.
” represents the best quality, and “/” represents the worst quality.

As a halftone dot original plate for plate making, dot quality "!" and "ri" are practically usable, "3" is poor but just barely practical, and "ko" and "/" are of impractical quality. It is a halftone dot.

1+-X-+-+ Black spots are observed through a microscope bowl! It is evaluated in stages, with "!" representing the best quality and "/" representing the worst quality. ``!'' or ``ri'' is practical, l'''3J is poor, but ``gishigi'' is practical, and ``2'' or ``/'' is not practical.

Comparative compound a From the above results, the compound of the present invention is compared to comparative compounds a and b.
It can be seen that even with a small amount of additive, it can give a high contrast gradation and the halftone dot quality is also excellent.

Furthermore, the compounds of the present invention have improved black spots compared to Comparative Compound C, and this effect is particularly remarkable in compounds with a large number of carbon atoms in the ballast portion.

Example C [Preparation of emulsion C] Silver nitrate aqueous solution and 1 mole of silver! ×/θ− A sodium chloride aqueous solution containing 6 mol of large ammonium rhodium(III) chloride was mixed in a gelatin solution at 4IO°C by the double jet method while controlling the pH to 1.3, and the average particle size was A monodisperse silver chloride emulsion of size 002 microns was prepared.

After particle formation, soluble salts are removed by flocculation methods well known in the art, and stabilizers such as terhydroxy-4-methyl-/, 3°3a, 7-thitraazaindene and/-7 Enyl J-mercaptotetrazole was added. How much gelatin is contained in emulsion/kg? J-g, silver was IOJ'g.

Dye Compound C Using Emulsion C, the compounds of the present invention shown in Table 2 and the above dye compound C (/70 mg/m2) were added, and λ,4t-dichloro-6-hydroxy- was added as a hardening agent. /
,! ,! Triazine sodium salt was added and a silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 3.1 g per 7 m2, and a gelatin layer was further coated as a protective layer on top of the silver halide emulsion layer. Photosensitive materials with sample numbers (J-/) to (Cho 70) were prepared.

Each photosensitive material was exposed through an optical wedge using a P-tiZDQ printer manufactured by Dainippon Screen Co., Ltd. (light source 100V, /kW quartz halogen lamp), then developed for 20 seconds at 5r0C with a developer having the same composition as in Example 1, and then developed using a conventional developer. It was fixed, washed and dried according to the method.

Measure the concentration of each sample that was currently processed and calculate the concentration.

The relative value of the exposure amount giving O was determined.

Each of the photosensitive materials with sample numbers (J-/) to (J-10) was used as safelight light using a Toshiba anti-fade fluorescent lamp (FLRao).
After leaving it for 0 to 60 minutes under the brightness of 00 lux of SW-DL-X NU/M), it was developed for 20 seconds at 1r0c with a developer having the same composition as in Example/, fixed, washed with water,
Dry.

The concentration of each sample obtained was measured, and the critical irradiation time at which the kabushi concentration of each sample began to increase was determined.

(The time limit was set as the time when the fog density increased by 0.02.) The results obtained are shown in Table 1.

From the results in Table 1, sample number (Korg) according to the present invention ~
The (λ-70) photosensitive material has a sensitivity that allows practical exposure and printing using a /kW quartz halogen lamp, and has excellent safelight safety under a fluorescent lamp that cuts off ultraviolet light.

-%1 The reciprocal of the exposure amount that gives the density q and θ is expressed as a relative value with sample number L2−/) as /θθ.

+f-2 Toshiba ■ anti-fading fluorescent light (FLR4tθ5W
-DL-X-NU/M) - When left under 〇〇lux, the limit irradiation time was shown in which the concentration of turnips remained within 10㎜, θ.

3 Units are expressed in moles per mole of silver.

Yoshi 4 γ represents the gradation of the characteristic curve as defined in Examples.

Yellow 5: 3r0 coated sample with developer having the same composition as Example/
After heating for 20 seconds, fixing, washing with water, drying, reswelling with water, press a sapphire pole with a diameter of θ, gmm onto the membrane surface with a needle glued to the tip, and transfer it to the needle while moving at a speed of rmrn/sec. It is expressed as the load (g) at which the membrane breaks (scratches occur) by changing the load continuously.

Screen 6 Comparative compounds a and b are the same compounds as in Example/.

Of particular note is that the compounds of the invention are comparable to comparative compound a
, b, the emulsion containing a large amount of Rh has a remarkable contrast-enhancing effect and a strong film strength.

Example 3 A photosensitive element was prepared by coating each layer in the following order on a polyethylene terephthalate transparent support.

(1) U.S. Patent No. 3. ! Polymer (3,0g/rn2) containing the following edge-reversing units in the following ratio in the copolymer described in the item 6H13 X:y=jθ:jO and gelatin (J, /m2) containing mordant layer.

(2) Titanium oxide θg/m2 and gelatinous.

0g/White reflective layer containing Tri Z.

(3) A light shielding layer containing 2.70 g/m2 of carbon black and 2.70 g/m2 of gelatin.

(4) The following magenta DRR compound (o, 4tzg/
m”), diethyl laurylamide (σ, 10g
/m2), j-di-t-butylhydrokino7 (0
,0074tg/m2), and gelatin (0.74g
/m2).

(5) Internal latent image emulsion (silver amount/, 4tg/
m2), containing green sensitizing dye (/, ?mg/m2) Table 3
The nucleating agent shown in and! - Interdecyl-hydroquinone-sodium cosulfonate (0, / / g/'m2)
green-sensitive internal latent image type direct positive silver iodobromide emulsion (silver iodide comolti) layer.

(6) A layer containing gelatin (o, 4tg/m2).

Processing was carried out using a combination of the above photosensitive elements/- and the following elements.

Treatment liquid The treatment liquid with the above composition was added to 0.0%. Each Ig was filled into a "pressure rupturable container".

Cover sheet Polyacrylic acid (70% by weight aqueous solution with a viscosity of 1,000 cp) as an acidic polymer layer (neutralizing layer) on a polyethylene tele7 tallate support and acetylcellulose (10,000 cp) as a neutralization timing layer.
Hydrolyze 0g of acetylcellulose! '? , 41
g/m2 and a copolymer of styrene and maleic anhydride (composition (mole) ratio, styrene: maleic anhydride = approx. to:<to, molecular weight approx.!
10,000) A cover sheet coated with Oo-g/m2 was prepared.

Forced deterioration conditions Two sets of the above photosensitive elements/- were prepared, and seven sets were stored in a refrigerator (r'
c), and the remaining amount/group is the temperature, IR'C relative humidity ♂O
It was left in S for q days.

Processing process The above cover sheet and the above photosensitive sheet were overlapped, and the color test chart was exposed from the side of the cover sheet, and then the above processing liquid was spread between both sheets to a thickness of 2 μm (spreading was done by applying pressure). (I did this with the help of a roller). The treatment was performed at 2j0C. After processing, the green density of nine strokes produced in the image-receiving layer was measured after processing/time using a Macbeth reflection densitometer through the transparent support of the photosensitive sheet.

The results are shown in Table 3.

Dmax: Maximum density of the positive image area of the product stored in the refrigerator SP: Density θ・! of the positive image area of the product stored in the refrigerator Relative sensitivity of (when S of photosensitive element - is /θθ) Sw: 3s'C relative humidity ♂θ% Density θ of positive image area of sample left for y days, relative sensitivity of j (S of photosensitive element -
Nucleating agent NA-1 NA-co As is clear from the above results, photosensitive elements 3 to 9 to which the nucleating agent of the present invention was added are different from photosensitive elements made by the conventional method. For λ and the same addition amount, I) max is likely to appear, and photosensitive elements 3~? It can be seen that there is little change in sensitivity when the photosensitive material is aged.

Example 9 (1) Preparation of hydrazine compound solution Solution A: Compound / at a concentration of θ! 70-
of water was dissolved in methanol.

Solution B: 10% of the compound so that the concentration is o, zcs.
Dissolved in methanol containing 1% water.

Solution C: Compound j is 70% so that the concentration is θ, /chi.
of water was dissolved in methanol.

Solution D: Compound/D was prepared by adding a methanol solution containing 70% water so that the concentration of Compound/D was 0°r%.

Solution E: Compound 24/ was dissolved in methanol to a concentration of σ,/%.

Solution F: A comparative compound was dissolved in methanol to a concentration of 2.

Comparative compound a (2) Preparation of light-sensitive material sample A cubic monodisperse silver iodobromide emulsion with an average grain size of 0.3 μm (
Silver iodide content: 2 mol %) was prepared, washed with water under normal pressure to remove soluble salts (E7), and chemically sensitized by adding sodium thiosulfate and potassium chloroaurate. This emulsion contained gelatin in an amount such that the gelatin/silver nitrate (weight ratio) was 0.30. This emulsion contains anhydro-j, j'-cyclolower-ethyl, ? as a sensitizing dye.
, J'-bis-(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added to give a-(N-methyl-N-
Oleoyl amino) ethanesulfonic acid sodium salt was added, and either of the above solutions A to E was added so that the amount of each hydrazine compound was 0 x 10-4 mol per mol of silver. Compare the amount of compound and F solution.The amount of compound is silver 1.
After adding the polyethyl acrylate dispersion to each of them, they were immediately heated at 1 or 3♂0C for 6
After stirring for an hour, hydroxyda as a hardening agent,
O-dichloro-/, J,! -) Sodium salt of riazine was added and coated on a polyethylene terephthalate film so that the amount of VC coated silver was 7.4 g/m2. At this time, a protective layer was applied at the same time.

(3) Evaluation method The sensitivity and gamma were evaluated by sensitometry in which each sample was exposed for 7 seconds under a light wedge.

The processing was carried out by developing with the following developer for 3r'C13o seconds, stopping, fixing, washing with water, and drying.

Developer hydroquinone ao, ogri, 4
t-dimethyl-/-phenyl-3-pyrazolidone o, 4tg sodium hydroxide /3. Ofg anhydrous potassium sulfite 90.0g tribasic potassium phosphate
7Q, 0g disodium ethylenediaminetetraacetate /, 0g potassium bromide 6. θg! -Methylbenzotriazole o, tg/-diethylaminoco, 3-dihydroxypropane /7.0g Add water /l (pH with potassium hydroxide//).

(adjust to j) The results are shown in Table 9.

As is clear from Table 9, when the comparison compound was added (AQ-4), the sensitivity and gamma significantly decreased as the coating solution aged after addition. In contrast, the samples of the present invention (A-Turf to a-j) showed good sensitivity and gamma both when added immediately before coating and when added 6 hours before coating. That is, it can be seen that the compounds of the present invention have excellent stability over time when added to photographic emulsions.

Example! Preparation of emulsion A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 3°q-dimethyl-/3-thiazoline-corchion per 1 mole of Ag, θ, zg, with vigorous stirring. ,! ! About 0C! They were added simultaneously over several minutes to obtain a monodisperse silver chlorobromide emulsion with an average grain size of approximately Q and λ μm (silver bromide content: 0 mol). 3 per mole of silver in this emulsion! mg sodium thiosulfate and 10
Chemical sensitization treatment was performed by adding mg of chloroauric acid (4 as hydrate) and heating at Z and ROC for 60 minutes.

In this way, the silver chlorobromide grains are used as cores and further grown by further treatment for 0 minutes in the same precipitation environment as the first time, and finally a monodisperse core/shell salt with an average particle diameter of 0° μm is formed. A silver bromide emulsion was obtained.

The coefficient of variation in particle size was approximately /θchi.

To this emulsion were added 3 mg of sodium thiosulfate (F) and 1.1 mg of chloroauric acid (4 as hydrate) per mole of silver,
At Otsuθ0C! A chemical sensitization treatment was performed by heating for θ minutes to obtain an internal latent image type silver halide emulsion.

A core/shell type autopositive emulsion was used on a paper support laminated on both sides with polyethylene. A multilayer color photographic paper having the layer structure shown in the table was prepared.

Table 5 (Layer composition) The composition of each layer is shown below. The numbers represent the coating amount per m2 in g. However, the amount of the nucleating agent applied per m2 is expressed in moles. Silver halide emulsions and colloidal silver are expressed in terms of coating amount in terms of silver, and spectral sensitizing dyes are expressed in moles as the amount added per 7 moles of silver halide.

Support polyethylene laminate paper [White pigment (T i O2
) and back dye (ulmarine)] 97th layer silver halide emulsion D θ, 26 Spectral sensitizing dye (ExSS-/) /, 0x10-4 Spectral sensitizing dye (ExSS-co) t, / ×10- 5 gelatin /, // cyan coupler (ExCC-/) 0.2/cyan coupler (ExCC-co) O,,2 as ultraviolet absorber (Ex
UV-/) 0, /7 solvent (ExS-/)
θ, 23 development regulator (ExGC-/
) 0, θλ stabilizer (ExA-/) 0. θ
θOtsu nucleation accelerator (ExZS-/) 3. oxlo-4 nucleating agent (EXZK-/) 3.5rx10-5 E colayer gelatin/, evening/color mixing inhibitor (ExKB-/) 0, θ desolvent (Ext
-/) θ, 10 solvent (ExS-2)
o, iθ E3rd layer silver halide emulsion D O,23 Spectral sensitizing dye (ExSS-,?) 3.0×/θ-4 Gelatin /, Q! Magenta coupler (ExMC-/) 0. /4-color image stabilizer (E
xSA-/) θ, coθ solvent (ExS-j)
θ・-25 development regulator (ExGC-/
) 0.0 co-stabilizer (ExA-/ )
0.004 Nucleation accelerator (EXZS-/) 2.7×
70-4 nucleating agent (ExZK-/) /, 4t x 10
-5 layer E4 gelatin 0.4t7 color mixing inhibitor (ExKB-/) 0.03 solvent (ExS
-/) θ, Oj solvent (ExS-co)
o, o3rd Ej layer Colloidal silver 0.09 Gelatin 0. <1 Color mixing prevention agent (E
xKB-/) 0.03 solvent (ExS-/)
0,03 solvent (BxS-J)
0.03 E6 layer Same as E4 layer 82nd layer Silver halide emulsion Do, aθ Spectral sensitizing dye (ExSS-j) Da, -X10-4 Gelatin Co, /2 Yellow coupler (ExYC-/) θ,! /solvent(ExS-
2) o, coθ solvent (ExS-Q)
0.20 Development control agent (ExGC-/)
0,0 stabilizer (EXA-/)
o, ooi nucleation accelerator (ExZS-/)! ,O×1
0-4-nucleating agent (EXZK −/) 2. oxio
-5th E/layer gelatin θ・j4 is UV absorber (ExUV-2) o, a solvent (EX
S-T) θ, ver E layer Gelatin /, Cor Acrylic modified copolymer of polyvinyl alcohol (Degree of modification/7 H) θ, /7 Liquid paraffin 0.03 Latex particles of polymethyl methacrylate (average particle Diameter λ, r μm) o,
or B/layer gelatin 1.70 B2 layer E? In addition to the above composition, a gelatin hardener ExGK-/
and surfactant were added.

Compounds used to prepare the sample (ExCC-/) Cyan turnip 2- α (ExCC-, 2) Cyan coupler (ExMC-/) Magenta coupler (CH2)3SO3H,N(C2H,)3(ExS
S-2) Spectral sensitizing dye (ExSS-3) Spectral sensitizing dye (ExSS-4z) Spectral sensitizing dye (E:r, S/) Solvent (ExS-,2) Solvent (ExS J) Solvent/: /Mixture (volume pressure) (ExS-4t) Solvent (ExUV-/) Ultraviolet absorber C4H9 (t) (1) : (2) : (3) j:/:R mixture (weight ratio) (ExUV-2 ) Ultraviolet absorber 2:9:r mixture of (1): (2)=(3) above (
Weight ratio) (ExSA-/) Color image stabilizer (ExKB-/) Color mixing inhibitor (ExGC-/) Development regulator (ExA-/) Stabilizer 1-Hydroxy! , 6-1-rimethylene-7゜J,j
&, 7-tetrazaindene (ExZS-/) nucleation promoter co(3-dimethylaminopropylthio)-! -Mercapto/, 3.41-thiadiazole hydrochloride (ExZK-/) Nucleating agent shown in Table 4.

(ExGK-/)gelatin hardener/-oxy-3,! -Dichloro-8-triazine sodium salt A multilayer silver halide color photographic light-sensitive material can be prepared by coating the coating solutions of E/layer E to E-th layer at the same time after adjusting the balance of surface tension and viscosity. The samples shown in Table 4 were prepared by applying pressure in this manner.

These samples were subjected to gradation exposure for sensitometry using an enlarger (Fujicolor Herad dθri, manufactured by Fuji Photo Film Co., Ltd.), and then developed using the following processing steps.

Processing step A Time Temperature color development 700 seconds 310C Bleach-fixing 30 seconds 310C Washing ■ 30 seconds 1r0c The replenishment method of washing water is so-called countercurrent flow in which the washing bath ■ is replenished and the overflow liquid from the washing bath ■ is led to the washing bath ■. It was a supplementary method.

[Color developer]

Diethylenetriaminepentaacetic acid 0.6g/-hydroxyethylidene-/,/-diphosphonic acid θ,! g diethylene glycol r, og benzyl alcohol, / 0, og sodium bromide
0.3g sodium chloride
θ・7g Sodium sulfite
Co,ogN,N-diethylhydroxylamine 3.3g3-methyl-deramino-N-ethyl-N-(β-methanesulfonamidoethyl) -Aniline 4.0gPotassium carbonate 30.0gAdd pure water
1000m100O10,! O pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 710g Sodium bisulfite 10g Ethylenediaminetetraacetic acid iron (In) ammonium cohydrate 4tOg
Ethylenediaminetetraacetic acid disodium cohydrate 7g 2-mercapto-1,3, add pure water and iooomit pH7
, O pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Pure water was used.

Here, pure water is water in which the concentrations of all cations other than hydrogen ions and all anions other than hydroxide ions in tap water are removed to /pprn or less by ion exchange treatment.

From the results shown in Table 6, it is clear that the compounds of the present invention have a superior ability to form color images when combined with an autopositive emulsion as shown in this example, compared to comparative compounds with similar structures.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment 1, case description Showa tco year patent application No. j♂jT13
No. 2, Title of the invention Silver halide photographic material 3
, Relationship with the case of the person making the amendment Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of "Detailed description of the invention" in the specification The description in the "Explanation" section has been amended as follows.

l) Page 12, line 3 After "alkyl group" "Aryl group" Insert all.

2) After "Applicable" on page 77, line j, insert "Among the substituents, mino group, sulfonylamino group, sulfamoyl group, and hydroxyl group are preferred."

3) No. 2F page? row "Phenoxyamide" "Phenoxycarbonylamino" and correct it.

Showa ≦3 years! Ri〆萱

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the emulsion layer containing at least one compound represented by the following general formula (I). A silver halide photographic material characterized by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfinic acid residue or an acyl group,
R_1 represents an aliphatic group, aromatic group, or heterocyclic group, R_2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group;
represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and Y represents a phenylene group or a naphthylene group. The total number of carbon atoms of R_1, R_2 and Y is 13 or more.